Plasticized aminoplast



Patented July 25, 1944 .PLASTICIZEU AMINOPLAST Gaetano F. DAlello, Pittlileld, Mass assignor to General Electric Company, a corporation of New York No Drawing. Application December 10, 1940, Serial No. 389,429

17 Claims.

This invention relates to new and useful compositions having properties that render them particularly useful in the plastics and coating arts. Specifically the invention is concerned with compositions of matter comprising an aminopiast (more particularly heat-curable and heat-cured aminoplasts) modified, specifically plasticized, with a nitrogenous compound selected from the class consisting of (l) aryl compounds having attached to the aryl nucleus at least one sulfonamide radical and at least one radical containing the essential unit I -SOzN- radicals and one, two or three ll -II-Y-C-NH 1 radicals, or one i SO1N- radical and one to five ll IIICI\'IH radicals, or one ll ITIC1TIH radical and one to five -SO2I I radicals. The unsatisfied single valencies in the described radicals may be satisfied by hydrogen or any monovalent organic compound, more particularly substituted or unsubstituted hydrocarbon radicals. The unsatisfied double valency of the carbon atom in the radical may be satisfied by a divalent atom-or radical, e. g., oxygen, sulfur, selenium, =NH, etc. The only requirement of the aryl compound is that it contains at least one N-substituted (partly or completely substituted) or N-unsubstituted sulfonamide radical and that there be attached to the nitrogen atom identified as N in formula (I) at least one hydrogen atom, as a result of which the compounds are reactable with an aldehyde, e. g., formaldehyde, and therefore can intercondense under heat with the other components of the aminoplast (or with the partially formed aminoplast) thereby to become an integral part of the resinous mass.

As is well known, aminoplasts are synthetic resins derived from amino (including imino) or amido (including imldo) compounds, a. typical example being urea-formaldehyde resin (reference: Modern Plastics, vol. 17, No. 2, October,

1939, page 433; U. S. Patent 2,214,851, DAlelio) Other examples of aminoplasts are aminotriazinealdehyde resins (e. g., melamine-formaldehyde resins), urea aminctriazine aldehyde resins aminodiazine-aldehyde resins, protein-aldehyde resins (e. g., casein-formaldehyde resins), aniline-aldehyde condensation products, benzene disulfonamide-aldehyde resins, sulfanilamide-aldehyde resins, resinous condensation products of aldehydes such as-formaldehyde with polyamides as, for instance, malonic diamide, maleic diamide, fumaric diamide, itaconic diamide, etc.

In the commercial utilization of aminoplasts in the plastics and coating arts, it is frequently necessary to modify the potentially heat-curable aminoplast by incorporating therein a plasticizer in order that the aminoplast will flow properly in the particular coating composition or, in the case of thermosetting 'aminoplasts molding compositions, will show good flow characteristics during molding. If improper or insufiicient plastic flow occurs during the molding operation, the molded articles may show streaked or wavy surfaces. Furthermore, if the plasticity of the molding composition is not suflicient, lack of physical homogeneity as the result of incompletely knitted granules often characterizes massive moldings.

From the foregoing it will be seen that particularly in the molding of heat-curable, plasticized aminoplasts it is important that the plasticizer have certain physical characteristics. It should improve the flow of the molding compound during molding without retarding the curing of the resin at molding temperatures. It should be compatible with 'the aminoplast both at normal and at elevated temperatures and should not "bleed" from the aminoplast' during or after molding. It should not discolor, or impart an odor to, or lessen the water resistance, electricaljproperties, me-

of urea decreases the water resistance or the molded article. Phenols impart color and odor, while aniline not only impartscolor and odor but also retards the cure of the resin during molding.

I have discovered that mono and poly aryl compounds having attached to the aryl nucleus at least one sulionamide radical and at least one radical containing the essential unit more particularly at least one ureido radical, and aldehyde-reaction products of such aryl compounds constitute a class of materials that meet 7 the above-mentioned requirements for a plasticizer for aminoplasts. These 'organic compolmds not only eiiectively plasticize the heatconvertible aminoplasts so thatthe aminoplast has good flow characteristics .during molding, but they accomplish this result without retarding the curing of the aminoplast during molding. Furthermore, the aminoplast' is intemally plasticized without any noticeable decrease in the other val ua'ble properties of the heat-hardened aminoplast, such as heatand water-resistance, dielectric strength, mechanical strength, surface appearance, color, odor, etc. Another advantage accruing from the use of these organic compounds is that they are able to intercondense with the potentially reactive aminoplast and, therefore, cannot "bleed from the molding composition or the molded article since they become an integral part of the resin molecule. Also. larger amounts of plasticizer can be tolerated in the compositions than usually has been possible with otherwise plasticized aminoplasts, and yet not impair the water resistance of the molded article. These results were quite surprising and unexpected, since in no way could it have been predicted from the known properties of these organic compounds or 01' aminoplasts that such compounds not only would serve eiiectively to 'plasticiz'e the heat-curable aminoplast but would do this without retarding its curing rate and without sacrifice of the useful properties 01' the cured aminoplast. This is all the more surprising when it is considered that closely related compounds, e. g.,

rnNc oNnOon where represents a mono or poly aromatic nucleus, e. g., benzene, halogeno aromatic (e. g., halogeno benzene), alkylated aromatic (e. g., alkylated benzene). hydroxylated aromatic (e. g., hydroxy benacne), alkoxy aromatic (e. g., alkoxy benzene), aryloxy aromatic (e. g., phcnoxy benzene), acetoxy aromatic (e. g., acetoxy benzene), carboalkoxy aromatic (e. g., carboalkoxy benzene), arylated benzene (e. g., phenyl benzene). naphthalene etc., nuclei. R may be either hydrogen or' a monovalent organic radical, more particularly a substituted or unsubstituted hydrocarbon radical, e. g., aryl (including naphthyl), aralkyl, alkyl, alkaryi, acyl, hydrocyclic, heterocycllc, etc., radicals, or nitro, halogeno, carboaikoxy, acetoxy, amido, imido, amino, nitrilo, etc., derivatives 0! such radicals. I prefer to use compounds where R represents hydrogen. Y may be a divalent atom or radical, examples of which have been given heretofore with reference to the unsatisfied double valency of the carbon atom to which Y i attached, but preferably is either oxyen or sulfur. In Formula (II) n and n are integers and each is at least 1, the sum of n and n varying from 2 up to the combining power of the particular aryl nucleus.

are entirely unsatisfactory, since not only do they More specific examples of compounds comprising the plasticizers used in carrying the present invention into effect are listed below:

Nnic ONHOS 0mm Nmc ONHGB OsNHCHr-ZH-O cm- HI 3 ONHI teachings of the present invention maybe de- (6 .NHIC ONE P|IHCONHN O:

S OsNHCHsCHiNHOrB 4 HaCNHCOE-O-S oiNnOs OINBI 'Nrnc ONEOS omnomonmnocomm cameo ONHOS mm lnmncomaG-somn,

- ll .NHIC ONHOS OZNHC-NH! mNmsONHc ONH C ,SO:NH2

Additional examples of compounds that may be employed are the aldehyde, specifically formaldehyde, reaction products of compounds such as above mentioned by way of illustration and wherein the l groups are converted into alkylol, specially methylol, derivatives, e. g., =NCR:OR, or alkylene, specifically methylene, derivatives, e. g.,

Example 1 A heat-convertible molding composition comprising 55-65 parts by weight potentially reactive urea-formaldehyde partial condensation product, a small amount of a curing reagent and 35-45 parts alpha cellulose in flock form were dried and ball milled with from 2 to parts of a ureidobenzenesulfonamide of the formula Nrnc ONHQS 0mm in the presence of the usual mold lubricants, dyes, etc. The finely ground powder was densified in the usual manner and molded at 130 to 150 C. under a pressure of about 2,000 pounds per square inch. In a similar way molding compositions composition.

and molded articles were prepared wherein the described plasticizer was omitted from the formulation. In all cases. better knitting and fusion took place and there was higher plastic flow per 'unit time in compositions containing the plasticizer as compared with the plasticizer-free Furthermore, there was no decrease in the water resistance of the molded article prepared from the described plasticized aminoplast.

In a specific case wherein 5% by weight (of the compound) of NH2CONHCeH4-BOzNH: was incorporated into a filled, plastioizer-free urea-formaldehyde molding compound, tests were made with a double-sphere photometer to determine the comparative light transmission of the plasticized and non-plasticized molded compounds in the form of thin disks. The improved translucency of the plasticized material is shown by the fact that it showed 28% light transmission, whereas the non-plasticized product transmitted only 4% light. The plasticizer-free compound showed practically no plastic fiow and did not knit or fuse together very well during molding. The plasticized compound, on the other hand, showed excellent plastic flow during molding and yielded molded articles that were well knitted or fused together into a strong molded piece or excellent surface characteristics.

Substantially the same results, as above described, are obtained when molding compositions comprising potentially reactive, filled melamineresins are substituted for the filled urea-formaldehyde molding composition.

More specific examples of aminoplasts which may be plasticized with the hereindescribed plasticizers are reaction products of aldehyde, for example formaldehyde or compounds engendering formaldehyde (e. g., paraformaldehyde, hexamethylene tetramine, etc.), with amido, imido, amino or imino compounds, or suitable mixtures thereof, for instance urea, thiourea, diurea, hydroxy urea, ethanol urea, unsymmetrical diphenyl urea, diethylene triurea, methyl urea, acetyl urea, phenyl thiourea, asymmetrical diethyl urea, allyl urea, 2-chloroallyl urea, ethylidene urea, methylol ureas, methylene ureas, guanidine, dicyandiamide, guanyl urea, guanyl thiourea, biguanide, aminodiazines, aminotriazines, aminodiazoles, creatinine, guanoline, etc. In many cases the use of an aminotriazine, e. g., melamine, alone or in conjunction with other amido, amino, imido or imino compounds, yields particularly valuable aminoplasts which may be internally modified in accordance with the present invention. Illustrative examples of aminotriazines that may be employed are given in various copending applications of mine, for example in copending application Serial No. 365,- 3'79, filed November 12, 1940, now Patent .No. 2,322,567, issued June 22, 1943, and assigned to the same assignee as the present invention. Suitable mixtures of aminotriazines also may be employed. All of these amido, imido, amino and imino compounds ,(amidogen compounds), are aldehyde-reactable and all contain at least one active 7 group.

dehyde, acrolein, methacrolein, crotonaldehyde, benzaldehyde, i'urfural, etc., mixtures thereof, or mixtures of formaldehyde (or compounds engendering formaldehyde) with such aldehydes.

As aminoplasts I prefer to use potentially heatcurable resinous reaction products of ingredients comprising, for example, urea and formaldehyde, or an aminotriazine (e. g., melamine), and form-* aldehyde, or. urea, melamine and formaldehyde. The hereindescribed plasticizer reactant or modifier may be incorporated into the resin along with the other reactants, or during or after formation of the partial condensation product, or during the preparation of the molding composition. For example, the plasticizer component may be incorporated into the resin or molding composition as described more specifically in, for example, my copending application Serial No.

346,962, filed July 23, 1940, now Patent No. 2,325,-

375, issued July 27, 1943, with particular. reference to suitable technique for incorporating a malonic ester into an aminoplast composition.

The potentially heat-convertible aminoplasts and molding (moldable) compositions containing the same may be prepared as described in the above-identified copending application and in various other 'copending applications, for example application Serial No,,'363,036, filed October 26, 1940, now Patent No. 2,320,817, issued June 1, 1943, and assigned to the same assignee as the present invention.

The amount of plasticizer reactant which is incorporated into the potentially reactive aminoplast or molding composition made therefrom ,may be varied as desired or as conditions may require, but ordinarily is employed in an amount corresponding approximately to from 0.1 to 10 or 12% by weight of the aminoplast, from 0.5 to 4 or being generally satisfactory for the usual aminoplasts,

Thermosetting molding compositions comprising potentially heat-curable aminoplasts plasticized with the piasticizer reactant herein described may be molded into a variety of shapes under heat and pressure, more particularly at temperatures of the order of 100 to 200 C., preferably from approximately 120 to 180 C. The plasticized compositions show good plastic fiow during molding. Molded articles of manufacture comprising the molded heat-hardened molding compositions of this invention have a good surface finish, show -no evidence of bleeding plasticizenare well cured throughout, and show no appreciable loss in any of their other useful properties due to the presence of the plasticizer. What I claim as new and desire to secure by Letters Patent of the United States is:

1. A composition of matter comprising an aminoplast modified with a nitrogenous compound selected from the class consisting of (1) aryl compounds having attached tothe aryl nucleus at least one sulfonamide radical and at least one ureido radical and (2) aldehyde-reaction products of the aryl compounds of (1').

2. A composition of matter comprising an aminoplast modified with a mono-aryl compound having attached to the aryl nucleus at least one sulfonamide radical and at least one ureido radical having at least one hydrogen atom attached directly to the terminal nitrogen atom, thereof.

3. A composition of matter comprising an aminoplast obtained by condensation of ingredients comprising a urea and an aldehyde, said aminoplast being modified with an aldehyde-reaction product of a mono-aryl compound having attached to the aryl nucleus at least one sulfonamide radical and at least one ureido radical having at least one hydrogen atom attached directly to the terminal nitrogen atom thereof.

4. A composition of matter comprising an aminoplast modified with a mono-aryl compound having attached to the aryl nucleus at least one sulfonamide radical and at least one radical ,having the structure NHCONH:.

5. A composition of matter comprising a potentially reactive aminoplast modified with a monoaryl compound having attached to the aryl nucleus at least one sulfonamide radical and at least one radical having the structure NHCONH:.

6. A composition of matter comprising an aminoplast produced by condensation of ingredients comprising a urea and an aldehyde, said aminoplast being modified with a mono-aryl compound having attached to the aryl nucleus a single SO:NH: radical and a single -NHCONH: radical.

7. A heat-curable composition comprising a potentially reactive aminoplast obtained by reaction of ingredients comprising urea and formaldehyde, said aminoplast being modified with a nitrogenous compound selected from the class consisting of (1) aryl compounds having attached to the aryl nucleus at least one sulfonamide radical and at least one ureido radical and (2) aldehyde-reaction products of the aryl compounds of 1).

8. A product comprising the cured composition of claim 7.

9. A heat-hardenable molding composition comprising a filler, a potentially reactive condensation product of ingredients comprising urea and formaldehyde, and a mono-arylcompound having attached to the aryl nucleus at least one sulfonamide radical and at least one radical having the structure --NHCONH:.

10. An article of manufacture comprising the heat-hardened molding composition of claim 9. 11. A composition comprising a condensation product of ingredients comprising urea and formaldehyde, and a modifier of said condensation product comprising an organic compound having the formula NH2CONHCeH4-SO:NH2.

12 A composition comprising a condensation product of ingredients comprising urea, melamine and formaldehyde, said condensation product beingmodified with an organic compound having the formula NHzCONH-CoHk-SOrNHz.

13. A composition comprising a condensation product of ingredients comprising urea and formaldehyde, and a modifier of said condensation product comprising an aldehyde-reaction product of an organic compound having the formula 14. A composition comprising a condensation product of ingredients comprising urea and foraldehyde, and a modifier of said condensation product comprising an organic compound having the formula" 15. The method of plasticizing an aminoplast obtained by reaction of ingredients comprising a urea and an aldehyde which comprises incorporating, under heat, into the said aminoplast in potentially reactive state a nitrogenous compound selected from the class consisting of (1) aryl compounds having attached to-the aryl nucleus at least one sulfonamide radical and at least one ureido radical and \2) aldehyde-reaction products of the aryl compounds of (1).

16. A composition comprising a-condensation product 0! ingredients comprising a urea and an aldehyde, said condensation product being modifled with a nitrogenous compound selected from the class consisting of (1) aryl compounds having attached to the aryl nucleus at least'one sulionamide radical and at least one ureido radical, 10

and (2) aldehyde-reaction products of the aryl compounds of (1). Y

17. A composition comprising a condensation product of ingredients comprising a urea, an aminotriazine and an aldehyde, said condensation product having intercondensed therein an aryl compound having attached to the aryl nucleus at least one sulfonamide radical and at least one ureido radical.

. GAETANO F. D'ALELIO. 

